Pentachlorophenol (PCP), as one of the common pesticide and preservatives, is easily accumulated in living organisms. Considering the high toxicity of PCP, the development of an effective and sensitive inspection method to determine the residual trace amounts of PCP continues to be a significant challenge. Herein, a convenient and sensitive electrochemical sensor is constructed by modifying glassy carbon electrode with cerium dioxide ( CeO2) nanoparticles anchored graphene ( CeO2-GR) to detect trace PCP. Benefiting from the two-dimensional lamellar structural advantages, the extraordinary electron-transfer properties, as well as the intensive coupling effect between CeO2 nanoparticles and graphene, the afforded CeO2- GR electrode nanomaterial possesses excellent electrocatalytic activity for the oxidation of PCP. Under the optimum synthetic conditions, the PCP oxidation peak currents of developed CeO2– GR sample exhibit a wide linear range of 5–150 μM. Moreover, the corresponding detection limit of PCP on the CeO2– GR electrode is as low as 0.5 μM. Apart from providing a promising electrochemical sensor, this work, most importantly, promotes an efficient route for the construction of highly active sensing electrode materials.